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Cas Database

74-98-6

74-98-6

Identification

  • Product Name:Propane

  • CAS Number: 74-98-6

  • EINECS:200-827-9

  • Molecular Weight:44.0965

  • Molecular Formula: C3H8

  • HS Code:2901100000

  • Mol File:74-98-6.mol

Synonyms:n-Propane;Dimethylmethane;HC 290;LPG;Liquefied petroleum gas;Propyl hydride;Purifrigor P 2;Purifrigor P 3;R 280;

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Safety information and MSDS view more

  • Pictogram(s):HighlyF+

  • Hazard Codes:F+

  • Signal Word:Danger

  • Hazard Statement:H220 Extremely flammable gas

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Artificial respiration may be needed. Refer for medical attention. In case of skin contact ON FROSTBITE: rinse with plenty of water, do NOT remove clothes. Refer for medical attention . In case of eye contact First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention. If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician. Vaporizing liquid may cause frostbite. Concentrations in air greater than 10% cause dizziness in a few minutes. 1% concentrations give the same effect in 10 min. High concentrations cause asphyxiation. (USCG, 1999) Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . Treat frostbite with rapid rewarming techniques ... ./Aliphatic hydrocarbons and related compounds/

  • Fire-fighting measures: Suitable extinguishing media Stop flow of gas. For small fires use dry chemicals. Cool adjacent areas with water spray. Behavior in Fire: Containers may explode. Vapor is heavier than air and may travel a long distance to a source of ignition and flash back. (USCG, 1999) Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Evacuate danger area! Consult an expert! Personal protection: self-contained breathing apparatus. Remove all ignition sources. Ventilation. NEVER direct water jet on liquid. Evacuate danger area! Consult an expert! Remove all ignition sources. Ventilation. NEVER direct water jet on liquid. (Extra personal protection: self-contained breathing apparatus.) ... Check oxygen content before entering area. Turn leaking cylinder with the leak up to prevent escape of gas in liquid state.

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Fireproof. Cool.COMPRESSED GASES MAY BE STORED IN THE OPEN ONLY IF THEY ARE ADEQUATELY PROTECTED FROM THE WEATHER & DIRECT SUNLIGHT. STORAGE AREAS SHOULD BE LOCATED AT A SAFE DISTANCE FROM OCCUPIED PREMISES & NEIGHBORING DWELLINGS. /GASES & AIR, COMPRESSED/

  • Exposure controls/personal protection:Occupational Exposure limit valuesRecommended Exposure Limit: 10 Hr Time-Weighted Avg: 1000 ppm (1800 mg/cu m).Biological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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Relevant articles and documentsAll total 985 Articles be found

Novel Rate Constants for a Catalytic Hydrogenation Reaction of Propylene Obtained by a Frequency Response Method

Yasuda, Yusuke,Iwai, Kayo,Takakura, Kazumi

, p. 17852 - 17861 (1995)

"Reaction rate (or FR) spectra" of a catalytic hydrogenation of propylene over Pt or Rh at 314 K were observed in a cell reactor composed of a proton-conducting membrane.It is shown that a variety of the spectra can be reproduced well by "characteristic functions", K*H(ω) and K*C(ω), which may be derived from a three-stage model composed of five elementary steps: X(g) -->/X(a) -->/X(a) --> propane (X: hydrogen or propylene), where X denotes the gaseous molecule; AX and BX are the first and second intermediate adsorbed species.Seven rate constants concerning these five steps were evaluated by matching K*H(ω) or K*C(ω) to the spectrum; five of them, kPX, k-AX, kAX, k-BX, and kBX, are ordinary rate constants, while the other two, l-BX and lBX, are novel ones.Since all these constants except kPX are independent of the amounts of catalyst, they are characteristic of active sites and can be compared with each other.On the basis of these constants, kinetic details have been discussed; for instance, mean residence times of AX and BX, τAX and τBX, respectively, were determined by (k-AX + kAX)-1 and (k-BX + kBX)-1, resulting in (in second units) τAH ca. 0.3 and τBH ca. 3 for hydrogen and τAC ca. 3 for propylene over Pt, while over Rh they were τAH ca. 1 and τBH ca. 3; τAC ca. 102 and τBC ca. 102.The nondimensional rate constants, l-BX and lBX, were indispensable to reproduce the various FR spectra; l-BH and lBH were positive, whereas l-BC and lBC were negative over both catalysts, which suggests heat effects.

Chemisorption and Surface Reactions in Cooperative Adsorption Systems.

Hesse

, p. 156 - 165 (1985)

The kinetics of propylene hydrogenation catalyzed by thermally treated supported platinum catalysts can be described by a Langmuir-Hinshelwood mechanism. The parameter values of the resulting rate equation, however, clearly depend on the coverage of the catalyst surface. Because of the instabilities observed with this reaction, it has to be assumed that lateral interaction of chemisorbed hydrogen and chemisorbed propylene is the main reason for this parameter variation. Using the lattice-gas model and the methods of statistical thermodynamics, straight-forward equations are derived which take into account the influence of this interaction on chemisorption and surface reaction in binary adsystems. The usefulness of these equations for the evaluation of kinetic measurements is demonstrated.

Frequency Response Method for the Study of Kinetics of a Heterogeneous Catalytic Reaction of Gases

Yasuda, Yusuke

, p. 7185 - 7190 (1989)

A new frequency response method is proposed on the basis of actual data on C3H6 + H2 -> C3H8 over Pt/Al2O3 at 273 K observed under each partial pressure of ca. 10 Pa: the gas space of a continuous-flow reactor was varied sinusoidally, and every partial pressure variation induced was followed by a mass spectrometer.Both amplitude and phase difference of ΔR observed in the angular frequency region from 40 to 60 rad/min were described well by , where Rs and PH(s) denote the overall reaction rate and the partial pressure of H2 at the steady state before the oscillation and is the time derivative of the pressure variation, dΔPH/dt.The "rate constant" n and κ were 0.15 and 7 * 1E-2 min, respectively.The unordinary rate equation involving PH was interpreted by R = ?dμd in terms of the driving force or the free energy drop, μd, and the frequency factor, ?d, at the rate-limiting step; Δ?d/?d = nΔPH/PH(s) and .The newly derived rate constant κ seemed to decrease with increasing temperature.The turnover frequency could be given by n/κ.

Organometallic complexes in supported ionic-liquid phase (SILP) catalysts: A PHIP NMR spectroscopy study

Gong, Qingxia,Klankermayer, Juergen,Bluemich, Bernhard

, p. 13795 - 13799 (2011)

para-Hydrogen induced polarization (PHIP) NMR spectroscopy emerges as an efficient and robust method for on-line monitoring of gas-phase hydrogenation reactions. Here we report detailed investigations of supported ionic liquid phase (SILP) catalysts in a continuous gas-phase hydrogenation of propene with PHIP NMR spectroscopy. A relocation of the rhodium complex in the thin layer of ionic liquid in the SILP catalyst at the initial stage of the propene hydrogenation is demonstrated. PHIP NMR spectroscopy can provide profound insight into the evolution of SILP catalysts during hydrogenation reactions.

Reductive dehalogenation of 1,3-dichloropropane by a [Ni(tetramethylcyclam)]Br2-Nafion modified electrode

Fontmorin,He,Floner,Fourcade,Amrane,Geneste

, p. 511 - 517 (2014)

Dechlorination reaction of 1,3-dichloropropane, a contaminant solvent, was investigated by electrochemical reduction in aqueous medium using a Ni(tmc)Br2complex, known as effective catalyst in dehalogenation reactions. The catalytic activity of the complex was first investigated by cyclic voltammetry and flow homogeneous redox catalysis using a graphite felt as working electrode. A total degradation of 1,3-dichloropropane was obtained after 5 h of electrolysis with a substrate/catalyst ratio of 2.3. The concentration of chloride ions determined by ion chromatography analysis showed a dechlorination yield of 98%. The complex was then immobilized on the graphite felt electrode in a Nafion film. Flow heterogeneous catalytic reduction of 1,3-dichloropropane was then carried out with the [Ni(tmc)]Br2-modified Nafion electrode. GC analyses underlined the total degradation of the substrate in only 3.5 h with a substrate/catalyst ratio of 100. A dechlorination yield of 80% was obtained, as seen with ion chromatography analyses of chloride ion. Comparison of both homogeneous and heterogeneous reactions highlighted the interest of the [Ni(tmc)]Br2-modified Nafion electrode that led to a higher stability of the catalyst with a turnover number of 180 and a higher current efficiency.

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Corner,Pease

, p. 564 (1945)

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In situ x-ray absorption spectroscopy and nonclassical catalytic hydrogenation with an iron(II) catecholate immobilized on a porous organic polymer

Kraft, Steven J.,Hu, Bo,Zhang, Guanghui,Miller, Jeffrey T.,Hock, Adam S.

, p. 3972 - 3977 (2013)

The oxidation state and coordination number of immobilized iron catecholate EtO2Fe(CAT-POP) were determined by X-ray absorption spectroscopy (XAS) under a variety of conditions. We find the as-prepared material to be three-coordinate Fe2+ that readily oxidizes to Fe3+ upon exposure to air but remains three-coordinate. Both the reduced and oxidized Fe(CAT-POP) catalyze olefin hydrogenation in batch and flow reactors. We determined the catalytic rates for both species and also observed by means of XAS that the oxidation state of the iron centers does not change in hydrogen at the reaction temperature. Therefore, we postulate that the mechanism of hydrogenation by Fe(CAT-POP) proceeds through one of several possible nonclassical mechanisms, which are discussed.

Podbielniak,Brown

, p. 773ff. (1929)

Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks

Shakya, Deependra M.,Ejegbavwo, Otega A.,Rajeshkumar, Thayalan,Senanayake, Sanjaya D.,Brandt, Amy J.,Farzandh, Sharfa,Acharya, Narayan,Ebrahim, Amani M.,Frenkel, Anatoly I.,Rui, Ning,Tate, Gregory L.,Monnier, John R.,Vogiatzis, Konstantinos D.,Shustova, Natalia B.,Chen, Donna A.

, p. 16533 - 16537 (2019)

We report the first study of a gas-phase reaction catalyzed by highly dispersed sites at the metal nodes of a crystalline metal–organic framework (MOF). Specifically, CuRhBTC (BTC3?=benzenetricarboxylate) exhibited hydrogenation activity, while other isostructural monometallic and bimetallic MOFs did not. Our multi-technique characterization identifies the oxidation state of Rh in CuRhBTC as +2, which is a Rh oxidation state that has not previously been observed for crystalline MOF metal nodes. These Rh2+ sites are active for the catalytic hydrogenation of propylene to propane at room temperature, and the MOF structure stabilizes the Rh2+ oxidation state under reaction conditions. Density functional theory calculations suggest a mechanism in which hydrogen dissociation and propylene adsorption occur at the Rh2+ sites. The ability to tailor the geometry and ensemble size of the metal nodes in MOFs allows for unprecedented control of the active sites and could lead to significant advances in rational catalyst design.

REDISPERSION OF COBALT METAL PARTICLES IN Co/TiO2 CATALYST AND ITS EFFECT ON PROPENE HYDROGENATION

Takasaki, Seiji,Takahashi, Kaoru,Suzuki, Hideo,Sato, Yuzuru,Ueno, Akifumi,Kotera, Toyohashi

, p. 265 - 268 (1983)

The rate of propene hydrogenation on Co/TiO2 catalyst, prepared by an alkoxide technique, was significantly enhanced when the catalyst was reduced by hydrogen at 700 deg C.However, over the catalyst prepared by an usual impregnation method, the enhancement of the rate was not observed at any reduction temperatures.The effects of reduction temperatures on the rate of propene hydrogenation were elucidated by redispersion of metallic cobalt particles.

Kinetic Determination of the Gas-Phase Decarbonylation of Butyraldehyde in the Presence of HCl Catalyst

Julio, Libia L.,Cartaya, Loriett,Maldonado, Alexis,Monascal, Yeljair,Mora, José R.,Cordova, Tania,Chuchani, Gabriel

, p. 333 - 338 (2017)

The gas-phase kinetics and mechanism of the homogeneous elimination of CO from butyraldehyde in the presence of HCl has been experimentally studied. The reaction is homogeneous and follows the second-order kinetics with the following rate expression: log k1 (s?1 L mol?1) = (13.27 ± 0.36) – (173.2 ± 4.4) kJ mol?1(2.303RT)?1. Experimental data suggested a concerted four-membered cyclic transition state type of mechanism. The first and rate-determining step occurs through a four-membered cyclic transition state to produce propane and formyl chloride. The formyl chloride intermediate rapidly decomposes to CO and HCl gases.

A stable 16-electron iridium(iii) hydride complex grafted on SBA-15: A single-site catalyst for alkene hydrogenation

Rimoldi, Martino,Fodor, Daniel,Van Bokhoven, Jeroen A.,Mezzetti, Antonio

, p. 11314 - 11316 (2013)

The dihydride pincer complex [IrH2(POCOP)] reacts with surface silanols of mesoporous silica (SBA-15) to give the coordinatively unsaturated, yet stable hydridesiloxo Ir(iii) species [IrH(O-SBA-15)(POCOP)]. The silica-grafted complex catalyses the hydrogenation of ethene and propene at low temperature and pressure without prior activation.

NATURE OF ACTIVITY AND SELECTIVITY OF CATALYSTS BASED ON DEALUMINIZED ZEOLITES. COMMUNICATION 2. ACTIVITY OF DEALUMINIZED Y ZEOLITES AND MORDENITE IN CRACKING STRAIGHT-CHAIN HYDROCARBONS

Tsybulevskii, A. M.,Klyachko, A. L.,Pluzhnikova, M. F.,Stepanova, I. N.,Brueva, T. R.,et al.

, p. 2395 - 2399 (1983)

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Direct synthesis of propylene oxide in the liquid phase under mild conditions

Kertalli,Schouten,Nijhuis

, p. 200 - 205 (2016)

Here, we study the direct synthesis of propylene oxide (PO) on Pd-based catalysts operating under mild conditions (40?°C, 5.5?bar) and in a continuous flow microreactor. We show that the PO yield can be improved by a factor of two, with respect to the values present in literature, by using a Pd–Pt/TS-1 catalyst in excess of oxygen. Moreover, we compare the PO reaction with the hydrogen peroxide (H2O2) synthesis, being H2O2 (or OOH species) the intermediate and rate limiting step of the direct PO formation. We found that the optimal conditions for the PO synthesis are not advantageous for the H2O2 productivity. In this respect, the presence of Pt, which improves the PO selectivity by lowering the hydrogenation of propylene, negatively affects the H2O2 productivity due to an acceleration of its side reactions. This effect is more pronounced for the Pd–Au/TS-1 catalyst, which shows a high performance for H2O2 production. However, the PO formation remains relatively poor due to a very fast hydrogenation of propylene to propane. We conclude that the optimization of the H2O2 synthesis is not sufficient to improve the direct PO formation. Indeed, the hydrogenation of propylene needs also to be considered.

RHODIUM-CATALYSED HYDROGENATION OF ALLENE AS REVEALED BY 14C>PROPYLENE AND 14C>CARBON MONOXIDE TRACER STUDIES

Kuhnen, Nivaldo C.,Thomson, Samuel J.,Webb, Geoffrey

, p. 2195 - 2210 (1983)

The low-pressure hydrogenation of allene has been studied over alumina-supported rhodium catalysts.During a series of hydrogenation reactions the activity of the catalyst progressively decreases to a steady-state value and thereafter remains constant.The reaction proceeds in two distinct stages.During the first stage the selectivity for the formation of propylene is ca. 95percent.Hydrogenation of allene+14C>propylene mixtures shows that, in the first stage allene hydrogenation, the yield of propane from the hydrogenation of propylene is relatively small.Direct hydrogenation of adsorbed allene to propane is the major route to formation of the latter, the selectivity being a measure of the relative rates of hydrogenation of allene directly to propylene and propane.Adsorption of 14C>propylene on freshly reduced catalysts occurs in two distinct stages: a non-linear primary region followed by a linear secondary region.No primary region is observed for propylene adsorption on steady-state catalysts or on freshly reduced catalysts in the presence of allene.However, 14C>propylene adsorption and hydrogenation occurs in the presence of allene on the secondary region with both freshly reduced and steady-state catalysts.Adsorption of 14C>carbon monoxide shows that, whilst the decrease in activity of the catalyst to a steady-state constant value corresponds to the progressive build-up of a surface hydrocarbonaceous layer, the combined effects of allene and hydrogen on a carbon monoxide-precovered surface leads to an increase in the capacity of that surface for carbon monoxide adsorption.Treatment of the carbon-monoxide-precovered surface with hydrogen alone does not lead to such an increase.It is suggested that, under the influence of the allene hydrogenation reaction, the surface undergoes some reconstruction.Evidence is presented to show the presence of separate surface site for the hydrogenation of allene to propane and for the hydrogenation of propylene to propane.

Wagner et al.

, p. 5786 (1950)

Kinetics of Propene Hydrogenation over Platinum and Platinum-Tin Catalysts Supported on Polyamide

Galvagno, Signorino,Staiti, Pietro,Antonucci, Pierluigi,Donato, Andrea,Pietropaolo, Rosario

, p. 2605 - 2612 (1983)

The rate of propene hydrogenation has been measured, in a flow system, over platinum supported on inorganic materials (Al2O3, MgO) and polyamides(Nylon 66 and Nylon 610).The effect of adding tin to Pt/Nylon 66 has also been investigated.The orders of reaction with respect to the reactants have been found to be strongly influenced by the nature of the support used.In particular, higher values of the reaction order with respect to propene have been found on Pt/Nylon samples.The presence of electron-deficient sites is suggested.Addition of Sn causes a drastic decrease in catalytic activity, suggesting Sn enrichment on the surface and/or an electronic interaction between the two metal components.

Obi,Tanaka

, p. 424 (1966)

Heterogeneous Parahydrogen Pairwise Addition to Cyclopropane

Salnikov, Oleg G.,Kovtunov, Kirill V.,Nikolaou, Panayiotis,Kovtunova, Larisa M.,Bukhtiyarov, Valerii I.,Koptyug, Igor V.,Chekmenev, Eduard Y.

, p. 2621 - 2626 (2018)

Hyperpolarized gases revolutionize functional pulmonary imaging. Hyperpolarized propane is a promising emerging contrast agent for pulmonary MRI. Unlike hyperpolarized noble gases, proton-hyperpolarized propane gas can be imaged using conventional MRI scanners with proton imaging capability. Moreover, it is non-toxic odorless anesthetic. Furthermore, propane hyperpolarization can be accomplished by pairwise addition of parahydrogen to propylene. Here, we demonstrate the feasibility of propane hyperpolarization via hydrogenation of cyclopropane with parahydrogen. 1H propane polarization up to 2.4 % is demonstrated here using 82 % parahydrogen enrichment and heterogeneous Rh/TiO2 hydrogenation catalyst. This level of polarization is several times greater than that obtained with propylene as a precursor under the same conditions despite the fact that direct pairwise addition of parahydrogen to cyclopropane may also lead to formation of propane with NMR-invisible hyperpolarization due to magnetic equivalence of nascent parahydrogen protons in two CH3 groups. NMR-visible hyperpolarized propane demonstrated here can be formed only via a reaction pathway involving cleavage of at least one C–H bond in the reactant molecule. The resulting NMR signal enhancement of hyperpolarized propane was sufficient for 2D gradient echo MRI of ~5.5 mL phantom with 1×1 mm2 spatial resolution and 64×64 imaging matrix despite relatively low chemical conversion of cyclopropane substrate.

Johnson,Walters

, p. 6266 (1954)

Robust In Situ Magnetic Resonance Imaging of Heterogeneous Catalytic Hydrogenation with and without Hyperpolarization

Kovtunov, Kirill V.,Lebedev, Dmitry,Svyatova, Alexandra,Pokochueva, Ekaterina V.,Prosvirin, Igor P.,Gerasimov, Evgeniy Y.,Bukhtiyarov, Valerii I.,Müller, Christoph R.,Fedorov, Alexey,Koptyug, Igor V.

, p. 969 - 973 (2019)

Magnetic resonance imaging (MRI) is a powerful technique to characterize reactors during operating catalytic processes. However, MRI studies of heterogeneous catalytic reactions are particularly challenging because the low spin density of reacting and product fluids (for gas phase reactions) as well as magnetic field inhomogeneity, caused by the presence of a solid catalyst inside a reactor, exacerbate already low intrinsic sensitivity of this method. While hyperpolarization techniques such as parahydrogen induced polarization (PHIP) can substantially increase the NMR signal intensity, this general strategy to enable MR imaging of working heterogeneous catalysts to date remains underexplored. Here, we present a new type of model catalytic reactors for MRI that allow the characterization of a heterogeneous hydrogenation reaction aided by the PHIP signal enhancement, but also suitable for the imaging of regular non-polarized gases. These catalytic systems permit exploring the complex interplay between chemistry and fluid-dynamics that are typically encountered in practical systems, but mostly absent in simple batch reactors. High stability of the model reactors at catalytic conditions and their fabrication simplicity make this approach compelling for in situ studies of heterogeneous catalytic processes by MRI.

Production of Propane and Other Short-Chain Alkanes by Structure-Based Engineering of Ligand Specificity in Aldehyde-Deformylating Oxygenase

Khara, Basile,Menon, Navya,Levy, Colin,Mansell, David,Das, Debasis,Marsh, E. Neil G.,Leys, David,Scrutton, Nigel S.

, p. 1204 - 1208 (2013)

Biocatalytic propane production: structure-based engineering of aldehyde-deformylating oxygenase improves specificity for short- and medium-chain-length aldehydes and enhances the propane generation in whole-cell biotransformations. This presents new opportunities for developing biocatalytic modules for the production of volatile "drop-in" biofuels.

Hoey,Le Roy

, p. 580 (1955)

Rhodium catechol containing porous organic polymers: Defined catalysis for single-site and supported nanoparticulate materials

Kraft, Steven J.,Zhang, Guanghui,Childers, David,Dogan, Fulya,Miller, Jeffrey T.,Nguyen, Sonbinh T.,Hock, Adam S.

, p. 2517 - 2522 (2014)

A single-site, rhodium(I) catecholate containing porous organic polymer was prepared and utilized as an active catalyst for the hydrogenation of olefins in both liquid-phase and gas-phase reactors. Liquid-phase, batch hydrogenation reactions at 50 psi and ambient temperatures result in the formation of rhodium metal nanoparticles supported within the polymer framework. Surprisingly, the Rh(I) complex is catalytically active and stable for propene hydrogenation at ambient temperatures under gas-phase conditions, where reduction of the Rh(I) centers to Rh(0) nanoparticles requires at least 200-250 °C under a flow of hydrogen gas. After high-temperature treatment, the Rh(0) nanoparticles are active arene hydrogenation catalysts that convert toluene to methylcyclohexadiene at a rate of 9.3 × 10-3 mol g-1 h-1 of rhodium metal at room temperature. Conversely, single-site Rh(I) is an active and stable catalyst for the hydrogenation of propylene (but not toluene) under gas-phase conditions at room temperature.

Tetrahedral Nickel(II) Phosphosilicate Single-Site Selective Propane Dehydrogenation Catalyst

Zhang, Guanghui,Yang, Ce,Miller, Jeffrey T.

, p. 961 - 964 (2018)

Silica-supported Ni catalysts usually show poor stability, low selectivity, and short lifetime in high-temperature alkane dehydrogenation reactions owing to the reduction to Ni0 nanoparticles under the reaction conditions. The introduction of a phosphate ligand to silica-supported NiII provided single-site tetrahedral NiII phosphosilicate as a stable and selective propane dehydrogenation catalyst. The NiII?OSi bonds activate the C?H bonds of propane and make the NiII sites catalytically active, whereas the Ni?OP bonds prevent the reduction of NiII to Ni0 under the dehydrogenation conditions and help to achieve high stability and selectivity.

Gordon,Heimel

, (1958)

Silica-Encapsulated Pt-Sn Intermetallic Nanoparticles: A Robust Catalytic Platform for Parahydrogen-Induced Polarization of Gases and Liquids

Zhao, Evan W.,Maligal-Ganesh, Raghu,Xiao, Chaoxian,Goh, Tian-Wei,Qi, Zhiyuan,Pei, Yuchen,Hagelin-Weaver, Helena E.,Huang, Wenyu,Bowers, Clifford R.

, p. 3925 - 3929 (2017)

Recently, a facile method for the synthesis of size-monodisperse Pt, Pt3Sn, and PtSn intermetallic nanoparticles (iNPs) that are confined within a thermally robust mesoporous silica (mSiO2) shell was introduced. These nanomaterials offer improved selectivity, activity, and stability for large-scale catalytic applications. Here we present the first study of parahydrogen-induced polarization NMR on these Pt-Sn catalysts. A 3000-fold increase in the pairwise selectivity, relative to the monometallic Pt, was observed using the PtSn@mSiO2 catalyst. The results are explained by the elimination of the three-fold Pt sites on the Pt(111) surface. Furthermore, Pt-Sn iNPs are shown to be a robust catalytic platform for parahydrogen-induced polarization for in vivo magnetic resonance imaging.

Role of Solid-state Structure in Propene Hydrogenation with Nickel Catalysts

Carturan, Giovanni,Enzo, Stefano,Ganzeria, Renzo,Lenarda, Maurizio,Zanoni, Roberto

, p. 739 - 746 (1990)

Various forms of Ni-based catalysts have been prepared by different synthetic procedures, affording ordinary f.c.c.Ni metal, a novel h.c.p.Ni allotrope and amorphous NiB powders.The samples were characterized by physical and chemical methods, including XPS, WAXS and SAXS analysis.These techniques provide detailed descriptions of the degree of oxidation of the metal surface and of the physical state of the bulk.The catalytic performance of each catalyst was tested in propene hydrogenation using a flow reactor under mild conditions.Data of intrinsic catalytic activity and activation energy were obtained and are discussed in relation to the morphology and solid state of the samples studied here.The intrinsic catalytic activity of h.c.p.Ni is much higher that that of f.c.c, suggesting the paramount importance of structural features in determining catalytic activity.

Yang

, p. 3795 (1962)

Separation of Anti-Phase Signals Due to Parahydrogen Induced Polarization via 2D Nutation NMR Spectroscopy

Obenaus, Utz,Althoff-Ospelt, Gerhard,Lang, Swen,Himmelmann, Robin,Hunger, Michael

, p. 455 - 458 (2017)

The present work introduces a novel method for the selective detection of 1H NMR anti-phase signals caused by the pairwise incorporation of parahydrogen into olefins on noble-metal-containing catalysts. Via a two-dimensional (2D) nutation NMR experiment, the anti-phase signals of hyperpolarized 1H nuclei are separated due to their double nutation frequency compared to that of thermally polarized 1H nuclei. For demonstrating this approach, parahydrogen induced polarization (PHIP) was achieved via the hydrogenation of propene with parahydrogen on platinum-containing silica and investigated by in situ 1H MAS NMR spectroscopy under continuous-flow conditions, that is, the hydrogenation reaction was performed inside the magnet of the NMR spectrometer. The 2D nutation NMR experiment described in the present work is useful for the separation of overlapping anti-phase and in-phase signals due to hyperpolarized and thermally polarized 1H nuclei, respectively, which is important for research in the field of heterogeneous catalysis.

Ultra-Low Loading Pt/CeO2 Catalysts: Ceria Facet Effect Affords Improved Pairwise Selectivity for Parahydrogen Enhanced NMR Spectroscopy

Song, Bochuan,Choi, Diana,Xin, Yan,Bowers, Clifford R.,Hagelin-Weaver, Helena

, p. 4038 - 4042 (2021)

Oxide supports with well-defined shapes enable investigations on the effects of surface structure on metal–support interactions and correlations to catalytic activity and selectivity. Here, a modified atomic layer deposition technique was developed to achieve ultra-low loadings (8–16 ppm) of Pt on shaped ceria nanocrystals. Using octahedra and cubes, which expose exclusively (111) and (100) surfaces, respectively, the effect of CeO2 surface facet on Pt-CeO2 interactions under reducing conditions was revealed. Strong electronic interactions result in electron-deficient Pt species on CeO2 (111) after reduction, which increased the stability of the atomically dispersed Pt. This afforded significantly higher NMR signal enhancement in parahydrogen-induced polarization experiments compared with the electron-rich platinum on CeO2 (100), and a factor of two higher pairwise selectivity (6.1 %) in the hydrogenation of propene than any previously reported monometallic heterogeneous Pt catalyst.

Investigation on the Thermal Cracking and Interaction of Binary Mixture of N-Decane and Cyclohexane

Chen, Xuejiao,Pang, Weiqiang,Wang, Bo,Zhang, Ziduan,Zhou, Lingxiao,Zhu, Quan

, (2022/03/02)

Abstract: The investigation about the thermal cracking performance and interaction of different components in hydrocarbon fuels is of great significance for optimizing the formulation of high-performance hydrocarbon fuels. In this work, thermal cracking of n-decane, cyclohexane and their binary mixture were studied in a tubular reactor under different temperatures and pressures. The gas and liquid products were analyzed in detail with different gas chromatography. The main gas products of pure n-decane and cyclohexane are similar, and there is a certain difference in the main liquid products. For binary mixture, the overall conversion rate and gas yield are lower than their theoretical value. The cracking conversion rate of n-decane in binary mixture is lower than that in pure n-decane, but the opposite change occurs for cyclohexane, and the effect become more obvious as the increase of the reaction pressure. These experimental phenomena can be explained by bond dissociation energy and free radical reaction mechanism. The pressure affects the free radical reaction path, and high pressure is more conducive to bimolecular hydrogen abstraction reaction, which will lead to different product content. A law of interaction between the n-decane and cyclohexane was observed according to the experimental results. [Figure not available: see fulltext.]

Conversion of Phenol and Lignin as Components of Renewable Raw Materials on Pt and Ru-Supported Catalysts

Bobrova, Nataliia A.,Bogdan, Tatiana V.,Bogdan, Viktor I.,Koklin, Aleksey E.,Mishanin, Igor I.

, (2022/03/01)

Hydrogenation of phenol in aqueous solutions on Pt-Ni/SiO2, Pt-Ni-Cr/Al2 O3, Pt/C, and Ru/C catalysts was studied at temperatures of 150–250? C and pressures of 40–80 bar. The possibility of hydrogenation of hydrolysis lignin in an aqueous medium in the presence of a Ru/C catalyst is shown. The conversion of hydrolysis lignin and water-soluble sodium lignosulfonate occurs with the formation of a complex mixture of monomeric products: a number of phenols, products of their catalytic hydrogenation (cyclohexanol and cyclohexanone), and hydrogenolysis products (cyclic and aliphatic C2 –C7 hydrocarbons).

Transformation synthesis of SSZ-13 zeolite from ZSM-35 zeolite

Bing, Liancheng,Cong, Wenwen,Han, Dezhi,Li, Kexu,Li, Qiang,Wang, Fang,Wang, Guangjian,Xu, Changyou

, (2021/10/06)

Interzeolite conversion as a promising alternative strategy for zeolite synthesis has received extensive attention. It is of great significance to understand the potential rules of conversion between zeolites with different topologies for effective regulation of zeolite synthesis. Hydrothermal conversion of ZSM-35 (FER-type) zeolite containing the mor composite building units into SSZ-13 zeolite (CHA-type) using N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdaOH) as template was performed for the first time. The effects of TMAdaOH/SiO2 ratio, Na2O/SiO2 ratio, the additional starting zeolite and crystallization time on the interzeolite conversion of ZSM-35 into SSZ-13 were investigated. The interzeolite conversion mechanism concerning the synthesis of SSZ-13 from ZSM-35 zeolite was proposed and verified by DFT calculation. The results of DFT calculations suggested that ZSM-35 zeolite with mor composite building unit had the potential to decompose into 6-Membered Rings, and further transform into CHA-type zeolite containing d6r composite building unit. Therefore, zeolites containing mor structure have the potential to be converted into zeolites containing d6r structure.

Heterogeneous Parahydrogen-Induced Polarization of Diethyl Ether for Magnetic Resonance Imaging Applications

Salnikov, Oleg G.,Svyatova, Alexandra,Kovtunova, Larisa M.,Chukanov, Nikita V.,Bukhtiyarov, Valerii I.,Kovtunov, Kirill V.,Chekmenev, Eduard Y.,Koptyug, Igor V.

supporting information, p. 1316 - 1322 (2020/12/14)

Magnetic resonance imaging (MRI) with the use of hyperpolarized gases as contrast agents provides valuable information on lungs structure and function. While the technology of 129Xe hyperpolarization for clinical MRI research is well developed, it requires the expensive equipment for production and detection of hyperpolarized 129Xe. Herein we present the 1H hyperpolarization of diethyl ether vapor that can be imaged on any clinical MRI scanner. 1H nuclear spin polarization of up to 1.3 % was achieved using heterogeneous hydrogenation of ethyl vinyl ether with parahydrogen over Rh/TiO2 catalyst. Liquefaction of diethyl ether vapor proceeds with partial preservation of hyperpolarization and prolongs its lifetime by ≈10 times. The proof-of-principle 2D 1H MRI of hyperpolarized diethyl ether was demonstrated with 0.1×1.1 mm2 spatial and 120 ms temporal resolution. The long history of use of diethyl ether for anesthesia is expected to facilitate the clinical translation of the presented approach.

Process route upstream and downstream products

Process route

1-(1-tert-Butylperoxy-1,2-dimethyl-propyl)-4-methoxy-benzene
186594-74-1

1-(1-tert-Butylperoxy-1,2-dimethyl-propyl)-4-methoxy-benzene

propane
74-98-6

propane

acetone
67-64-1

acetone

1-(4-methoxyphenyl)ethanone
100-06-1

1-(4-methoxyphenyl)ethanone

2,2,3-Trimethyl-3-(4-methoxyphenyl)-oxiran

2,2,3-Trimethyl-3-(4-methoxyphenyl)-oxiran

<i>tert</i>-butyl alcohol
75-65-0

tert-butyl alcohol

Conditions
Conditions Yield
With Isopropylbenzene; at 120 ℃; Rate constant; Product distribution; Thermodynamic data; var. of solvent, temp., ΔH(excit.), ΔS(excit.);
90.2 mmol
5.7 mmol
14.5 mmol
82.9 mmol
57 mmol
39 mmol
Conditions
Conditions Yield
at 1000 - 1100 ℃; under 820.855 Torr;
12.6 %Chromat.
3.39 %Chromat.
26 %Chromat.
0.35 %Chromat.
0.49 %Chromat.
15.1 %Chromat.
4.02 %Chromat.
3.65 %Chromat.
2.95 %Chromat.
4.85 %Chromat.
2.33 %Chromat.
0.77 %Chromat.
aluminum oxide; iron(III) oxide; at 1000 - 1100 ℃; under 820.855 Torr;
16.53 %Chromat.
4.01 %Chromat.
31.78 %Chromat.
0.49 %Chromat.
0.5 %Chromat.
16.02 %Chromat.
4.71 %Chromat.
0.76 %Chromat.
0.54 %Chromat.
4.2 %Chromat.
3.05 %Chromat.
1.06 %Chromat.
Conditions
Conditions Yield
zeolite ZSM-5; at 550 ℃; under 1500.15 Torr;
0.41%
1.22%
4.59%
2.24%
40.79%
11.83%
3.57%
6.01%
25.26%
Conditions
Conditions Yield
With zeolite ZSM-5; at 550 ℃; under 1500.15 Torr;
0.24%
0.73%
4.87%
2.13%
18.17%
7.03%
2.12%
3.57%
59.03%
zeolite ZSM-5; at 550 ℃; under 1500.15 Torr;
0.39%
1.15%
5.2%
2.24%
28.73%
11.11%
3.35%
5.65%
37.4%
C10+ aromatic compounds; ethyltoluene; toluene; trimethylbenzene; mixture of

C10+ aromatic compounds; ethyltoluene; toluene; trimethylbenzene; mixture of

A10 aromatics

A10 aromatics

A11+ aromatics

A11+ aromatics

butanes and pentanes

butanes and pentanes

ethane
74-84-0

ethane

propane
74-98-6

propane

ethylbenzene
100-41-4,27536-89-6

ethylbenzene

xylenes

xylenes

Conditions
Conditions Yield
With hydrogen; ITQ-13 zeolite containing 0.3percent Re; at 400 ℃; under 18751.9 Torr; Product distribution / selectivity;
5.5%
26.4%
2.9%
1.42%
1.7%
0.04%
1.85%
1.46%
0.98%
With hydrogen; Beta zeolite containing 0.3percent Re; at 400 ℃; under 18751.9 Torr; Product distribution / selectivity;
5.5%
25.9%
3.2%
0.54%
1.9%
0.12%
1.8%
3.45%
4.21%
Conditions
Conditions Yield
MoV0.15P0.10Fe0.11Cr0.16La0.06O(x); In water; at 650 ℃; under 1125.11 Torr; Product distribution / selectivity;
30.27%
14.88%
MoV0.15P0.10Fe0.11Zn0.12Ce0.08O(x); In water; at 650 ℃; under 1125.11 Torr; Product distribution / selectivity;
30.86%
14.53%
propane
74-98-6

propane

o-xylene
95-47-6

o-xylene

1-Methyl-3-ethylbenzene
620-14-4

1-Methyl-3-ethylbenzene

para-xylene
106-42-3

para-xylene

ethylbenzene
100-41-4,27536-89-6

ethylbenzene

1,2,4-Trimethylbenzene
95-63-6

1,2,4-Trimethylbenzene

Conditions
Conditions Yield
With zeolite H-ZSM-5 (Si/Al = 30); at 300 ℃; for 1.5h; under 760.051 Torr;
dibenzofuran
132-64-9,214827-48-2

dibenzofuran

cyclohexenone
930-68-7

cyclohexenone

2-Methylcyclopentanone
1120-72-5

2-Methylcyclopentanone

diphenylether
101-84-8

diphenylether

tert-butylbenzene
253185-03-4,253185-04-5

tert-butylbenzene

propane
74-98-6

propane

hexane
110-54-3

hexane

n-hexan-2-one
591-78-6

n-hexan-2-one

2-methyl-2-cyclopenten-1-one
1120-73-6

2-methyl-2-cyclopenten-1-one

n-pentylcyclohexane
4292-92-6

n-pentylcyclohexane

ethylbenzene
100-41-4,27536-89-6

ethylbenzene

1-butylbenzene
104-51-8

1-butylbenzene

pentylbenzene
538-68-1

pentylbenzene

cyclopentylbenzene
700-88-9

cyclopentylbenzene

4-Phenylphenol
92-69-3

4-Phenylphenol

dicyclohexyl ether
4645-15-2

dicyclohexyl ether

2-phenylpentane
2719-52-0

2-phenylpentane

1-pentenylbenzene
826-18-6

1-pentenylbenzene

2-butylcyclohexanone
1126-18-7

2-butylcyclohexanone

cyclohexylphenyl ether
2206-38-4

cyclohexylphenyl ether

2-cyclohexylphenol
119-42-6

2-cyclohexylphenol

3-methyl-phenol
108-39-4

3-methyl-phenol

ortho-cresol
95-48-7,77504-84-8

ortho-cresol

2-Phenylphenol
90-43-7,287950-96-3

2-Phenylphenol

cyclohexene
110-83-8

cyclohexene

cyclohexanol
108-93-0

cyclohexanol

Conditions
Conditions Yield
With hydrogen; 1 wtpercent K/1 wtpercent Pt/SiO2; at 425 ℃; under 5931.67 Torr;
dibenzofuran
132-64-9,214827-48-2

dibenzofuran

cyclohexenone
930-68-7

cyclohexenone

2-Methylcyclopentanone
1120-72-5

2-Methylcyclopentanone

diphenylether
101-84-8

diphenylether

tert-butylbenzene
253185-03-4,253185-04-5

tert-butylbenzene

propane
74-98-6

propane

hexane
110-54-3

hexane

ethylbenzene
100-41-4,27536-89-6

ethylbenzene

pentylbenzene
538-68-1

pentylbenzene

cyclopentylbenzene
700-88-9

cyclopentylbenzene

4-Phenylphenol
92-69-3

4-Phenylphenol

dicyclohexyl ether
4645-15-2

dicyclohexyl ether

cyclohexylphenyl ether
2206-38-4

cyclohexylphenyl ether

2-cyclohexylphenol
119-42-6

2-cyclohexylphenol

ortho-cresol
95-48-7,77504-84-8

ortho-cresol

2-Phenylphenol
90-43-7,287950-96-3

2-Phenylphenol

cyclohexene
110-83-8

cyclohexene

cyclohexanol
108-93-0

cyclohexanol

Conditions
Conditions Yield
With hydrogen; 1 wtpercent K/1 wtpercent Pt/SiO2; at 425 ℃; under 5931.67 Torr;
Dimethyl ether
115-10-6,157621-61-9

Dimethyl ether

methanol
67-56-1

methanol

2-methyl-but-2-ene
513-35-9

2-methyl-but-2-ene

butene-2
107-01-7

butene-2

ethane
74-84-0

ethane

propane
74-98-6

propane

methylbutane
78-78-4

methylbutane

2-Methylpentane
107-83-5

2-Methylpentane

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

carbon monoxide
201230-82-2

carbon monoxide

hydrogen
1333-74-0

hydrogen

2-pentene
109-68-2

2-pentene

Conditions
Conditions Yield
With water; at 330 - 360 ℃; under 760.051 Torr; Temperature;

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